Efficient photocatalysis with graphene oxide/Ag/Ag2S–TiO2 nanocomposites under visible light irradiation

Lack of visible light response and low quantum yield hinder the practical application of TiO₂ as a high-performance photocatalyst. Herein, we present a rational design of TiO₂ nanorod arrays (NRAs) decorated with Ag/Ag₂S nanoparticles (NPs) synthesized through successive ion layer adsorption and reaction (SILAR) and covered by graphene oxide (GO) at room temperature. Ag/Ag₂S NPs with uniform sizes are well-dispersed on the TiO₂ nanorods (NRs) as evidenced by electron microscopic analyses. The photocatalyst GO/Ag/Ag₂S decorated TiO₂ NRAs shows much higher visible light absorption response, which leads to remarkably enhanced photocatalytic activities on both dye degradation and photoelectrochemical (PEC) performance. Its photocatalytic reaction efficiency is 600% higher than that of pure TiO₂ sample under visible light. This remarkable enhancement can be attributed to a synergy of electron-sink function and surface plasmon resonance (SPR) of Ag NPs, band matching of Ag₂S NPs, and rapid charge carrier transport by GO, which significantly improves charge separation of the photoexcited TiO₂. The photocurrent density of GO/Ag/Ag₂S–TiO₂ NRAs reached to maximum (i.e. 6.77 mA cm⁻²vs. 0 V). Our study proves that the rational design of composite nanostructures enhances the photocatalytic activity under visible light, and efficiently utilizes the complete solar spectrum for pollutant degradation.

The photocatalytic reaction efficiency of GO/Ag/Ag₂S–TiO₂ nanorod arrays is 600% higher than that of a pure TiO₂ sample under visible light.     

Copper(ii)-catalyzed synthesis of multisubstituted indoles through sequential Chan–Lam and cross-dehydrogenative coupling reactions

Starting from arylboronic acids and ester (Z)-3-aminoacrylates, one-pot syntheses of diverse indole-3-carboxylic esters have been described through copper(ii)-catalyzed sequential Chan–Lam N-arylation and cross-dehydrogenative coupling (CDC) reactions. The initial Chan–Lam arylation can proceed in DMF at 100 °C for 24 h to give ester (Z)-3-(arylamino)acrylate intermediates in the presence of Cu(OAc)₂/tri-tert-butylphosphine tetrafluoroborate, a catalytic amount of myristic acid as the additive, KMnO₄ and KHCO₃. Sequentially, these in situ arylated intermediates can undergo an intramolecular oxidative cross-dehydrogenative coupling process in mixed solvents (DMF/DMSO = 2 : 1) at 130 °C to give C3-functionalized multi-substituted indole derivatives.

One-pot syntheses of diverse indole-3-carboxylic esters have been described through copper(ii)-catalyzed sequential oxidative Chan–Lam N-arylation and cross-dehydrogenative coupling (CDC) reaction.     

Enhanced visible-light photodegradation of fluoroquinolone-based antibiotics and E. coli growth inhibition using Ag–TiO2 nanoparticles

Antibiotics in wastewater represent a growing and worrying menace for environmental and human health fostering the spread of antimicrobial resistance. Titanium dioxide (TiO₂) is a well-studied and well-performing photocatalyst for wastewater treatment. However, it presents drawbacks linked with the high energy needed for its activation and the fast electron–hole pair recombination. In this work, TiO₂ nanoparticles were decorated with Ag nanoparticles by a facile photochemical reduction method to obtain an increased photocatalytic response under visible light. Although similar materials have been reported, we advanced this field by performing a study of the photocatalytic mechanism for Ag–TiO₂ nanoparticles (Ag–TiO₂ NPs) under visible light taking in consideration also the rutile phase of the TiO₂ nanoparticles. Moreover, we examined the Ag–TiO₂ NPs photocatalytic performance against two antibiotics from the same family. The obtained Ag–TiO₂ NPs were fully characterised. The results showed that Ag NPs (average size: 23.9 ± 18.3 nm) were homogeneously dispersed on the TiO₂ surface and the photo-response of the Ag–TiO₂ NPs was greatly enhanced in the visible light region when compared to TiO₂ P25. Hence, the obtained Ag–TiO₂ NPs showed excellent photocatalytic degradation efficiency towards the two fluoroquinolone-based antibiotics ciprofloxacin (92%) and norfloxacin (94%) after 240 min of visible light irradiation, demonstrating a possible application of these particles in wastewater treatment. In addition, it was also proved that, after five Ag–TiO₂ NPs re-utilisations in consecutive ciprofloxacin photodegradation reactions, only a photocatalytic efficiency drop of 8% was observed. Scavengers experiments demonstrated that the photocatalytic mechanism of ciprofloxacin degradation in the presence of Ag–TiO₂ NPs is mainly driven by holes and ˙OH radicals, and that the rutile phase in the system plays a crucial role. Finally, Ag–TiO₂ NPs showed also antibacterial activity towards Escherichia coli (E. coli) opening the avenue for a possible use of this material in hospital wastewater treatment.

Ag nanoparticles decorated-TiO₂ P25 are a viable alternative for the degradation, through a rutile-mediated mechanism, of fluoroquinolone-based antibiotics under visible light irradiation and, at the same time, for bacteria inactivation in water.     

UCN–SiO2–GO: a core shell and conjugate system for controlling delivery of doxorubicin by 980 nm NIR pulse

Herein, graphene oxide (GO) has been attached with core–shell upconversion-silica (UCN–SiO₂) nanoparticles (NPs) to form a GO–UCN–SiO₂ hybrid nanocomposite and used for controlled drug delivery. The formation of the nanocomposite has been confirmed by various characterization techniques. To date, a number of reports are available on GO and its drug delivery applications, however, the synergic properties that arise due to the combination of GO, UCNPs and SiO₂ can be used for controlled drug delivery. New composite UCN@SiO₂–GO has been synthesized through a bio-conjugation approach and used for drug delivery applications to counter the lack of quantum efficiency of the upconversion process and control sustained release. A model anticancer drug (doxorubicin, DOX) has been loaded to UCNPs, UCN@SiO₂ NPs and the UCN@SiO₂–GO nanocomposite. The photosensitive release of DOX from the UCN@SiO₂–GO nanocomposite has been studied with 980 nm NIR laser excitation and the results obtained for UCNPs and UCN@SiO₂ NPs compared. It is revealed that the increase in the NIR laser irradiation time from 1 s to 30 s leads to an increase in the amount of DOX release in a controlled manner. In vitro studies using model cancer cell lines have been performed to check the effectiveness of our materials for controlled drug delivery and therapeutic applications. Obtained results showed that the designed UCN@SiO₂–GO nanocomposite can be used for controlled delivery based therapeutic applications and for cancer treatment.

A GO–UCN–SiO₂ hybrid nanocomposite for loading of doxorubicin and its use in in vitro efficiency for killing carcinoma cells.     

Construction of Cu–Ce/graphene catalysts via a one-step hydrothermal method and their excellent CO catalytic oxidation performance

Cu–Ce/graphene catalysts show high dispersion of metal particles and excellent activity and stability for catalytic oxidation. In this study, a hydrothermal method was used to synthesize a series of bimetallic Cu–Ce/graphene catalysts, and the effects of the proportions of Cu and Ce on CO oxidation were investigated in detail. Indispensable characterizations such as XPS, XRD, TEM, BET, and H₂-TPR were conducted to explore the effect of the Cu/Ce molar ratio and the metal valence on the activity and determine the structure–performance relationship. The results showed that bimetallic supported catalysts, such as 3Cu5Ce/graphene, 1Cu1Ce/graphene, and 5Cu3Ce/graphene, possessed significant catalytic activity. Especially, the 5Cu3Ce/graphene catalyst showed highest catalytic activity for CO oxidation, the T₁₀₀ value was 132 °C, and the apparent activation energy was 68.03 kJ mol⁻¹. Furthermore, the stability of the 5Cu3Ce/graphene catalyst was outstanding, which could be maintained for at least 12 h. Moreover, the CeO₂ particles were well crystalline with the size 5–9 nm in these catalysts, and the CuO nanoparticles were well dispersed on CeO₂ and graphene. Notably, the ratio of Cu/Ce in the catalyst was higher, the interaction between the Ce species and the graphene was stronger, and the Cu species were more easily reduced; this was beneficial for the oxidation of CO.

Cu–Ce/graphene catalysts show high dispersion of metal particles and excellent activity and stability for catalytic oxidation.     

Explosives sensing using Ag–Cu alloy nanoparticles synthesized by femtosecond laser ablation and irradiation

Herein we demonstrate the synthesis of Ag–Cu alloy NPs through a consecutive two-step process; laser ablation followed by laser irradiation. Initially, pure Ag and Cu NPs were produced individually using the laser ablation in liquid technique (with ∼50 femtosecond pulses at 800 nm) which was followed by laser irradiation of the mixed Ag and Cu NPs in equal volume. These Ag, Cu, and Ag–Cu NPs were characterised by UV-visible absorption, HRTEM and XRD techniques. The alloy formation was confirmed by the presence of a single surface plasmon resonance peak in absorption spectra and elemental mapping using FESEM techniques. Furthermore, the results from surface enhanced Raman scattering (SERS) studies performed for the methylene blue (MB) molecule suggested that Ag–Cu alloy NPs demonstrate a higher enhancement factor (EF) compared to pure Ag/Cu NPs. Additionally, SERS studies of Ag–Cu alloy NPs were implemented for the detection of explosive molecules such as picric acid (PA – 5 μM), ammonium nitrate (AN – 5 μM) and the dye molecule methylene blue (MB – 5 nM). These alloy NPs exhibited superiority in the detection of various analyte molecules with good reproducibility and high sensitivity with EFs in the range of 10⁴ to 10⁷.

Herein we demonstrate the synthesis of Ag–Cu alloy NPs through a consecutive two-step process; laser ablation followed by laser irradiation.     

Microstructure–mechanical properties of Ag0/Au0 doped K–Mg–Al–Si–O–F glass-ceramics

In understanding the catalytic efficacy of silver (Ag⁰) and gold (Au⁰) nanoparticles (NPs) on glass-ceramic (GC) crystallization, the microstructure–machinability correlation of a SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ system is studied. The thermal parameters viz., glass transition temperature (T_g) and crystallization temperature (T_c) were extensively changed by varying NPs (in situ or ex situ). Tc was found to be increased (T_c = 870–875 °C) by 90–110 °C when ex situ NPs were present in the glass system. Under controlled heat-treatment at 950 ± 10 °C, the glasses were converted into glass-ceramics with the predominant presence of crystalline phase (XRD) fluorophlogopite mica, [KMg₃(AlSi₃O₁₀)F₂]. Along with the secondary phase enstatite (MgSiO₃), the presence of Ag and Au particles (FCC system) were identified by XRD. A microstructure containing spherical crystallite precipitates (∼50–400 nm) has been observed through FESEM in in situ doped GCs. An ex situ Ag doped GC matrix composed of rock-like and plate-like crystallites mostly of size 1–3 μm ensured its superior machinability. Vicker''s and Knoop microhardness of in situ doped GCs were estimated within the range 4.45–4.61 GPa which is reduced to 4.21–4.34 GPa in the ex situ Ag system. Machinability of GCs was found to be in the order, ex situ Ag > ex situ Au ∼ in situ Ag > in situ Au. Thus, the ex situ Ag/Au doped SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ GC has potential for use as a machinable glass-ceramic.

In understanding the catalytic efficacy of silver (Ag⁰) and gold (Au⁰) nanoparticles (NPs) on glass-ceramic (GC) crystallization, the microstructure–machinability correlation of a SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ system is studied.     

Improvement of low-temperature NH3-SCR catalytic performance over nitrogen-doped MOx–Cr2O3–La2O3/TiO2–N (M = Cu,Fe, Ce) catalysts

A series of MO_x–Cr₂O₃–La₂O₃/TiO₂–N (M = Cu, Fe, Ce) catalysts with nitrogen doping were prepared via the impregnation method. Comparing the low-temperature NH₃-SCR activity of the catalysts, CeCrLa/Ti–N (xCeO₂–yCr₂O₃–zLa₂O₃/TiO₂–N) exhibited the best catalytic performance (NO conversion approaching 100% at 220–460 °C). The physico-chemical properties of the catalysts were characterized by XRD, BET, SEM, XPS, H₂-TPR, NH₃-TPD and in situ DRIFTS. From the XRD and SEM results, N doping affects the crystalline growth of anatase TiO₂ and MO_x (M = Cu, Fe, Ce, Cr, La) which were well dispersed over the support. Moreover, the doping of N promotes the increase of the Cr⁶⁺/Cr ratio and Ce³⁺/Ce ratio, and the surface chemical adsorption oxygen content, which suggested the improvement of the redox properties of the catalyst. And the surface acid content of the catalyst increased with the doping of N, which is related to CeCrLa/TiO₂–N having the best catalytic activity at high temperature. Therefore, the CeCrLa/TiO₂–N catalyst exhibited the best NH₃-SCR performance and the redox performance of the catalysts is the main factor affecting their activity. Furthermore, in situ DRIFTS analysis indicates that Lewis-acid sites are the main adsorption sites for ammonia onto CeCrLa/TiO₂–N and the catalyst mainly follows the L–H mechanism.

A series of MO_x–Cr₂O₃–La₂O₃/TiO₂–N (M = Cu, Fe, Ce) catalysts with nitrogen doping were prepared via the impregnation method.     

Design of GO–Ag-functionalized Fe3O4@CS composite for magnetic adsorption of rhodamine B

In this study, a novel magnetic composite (Fe₃O₄@CS/GO/Ag) modified with chitosan (CS), graphene oxide (GO) and Ag nanoparticles (Ag NPs) was successfully prepared as an efficient adsorbent for detection of rhodamine B (RB) combined with a fluorescence technique. The properties of the magnetic composite were confirmed by field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and vibrating sample magnetometry. The components of Fe₃O₄@CS/GO/Ag endowed it with excellent extraction performance and convenient operation. The main parameters affecting extraction and desorption efficiency were all investigated systematically. Under the optimized experimental conditions, the proposed method showed linear ranges (0.2–6.0 μg L⁻¹) with R² = 0.9992. The limits of detection (LODs) and quantification (LOQs) were 0.05 and 0.2 μg L⁻¹ (n = 3), respectively. Fe₃O₄@CS/GO/Ag exhibited outstanding extraction efficiency for RB, compared with CS-coated Fe₃O₄ nanoparticles (Fe₃O₄@CS) and GO-modified Fe₃O₄@CS (Fe₃O₄@CS/GO). The applicability of the proposed method was investigated by analyzing four real samples (waste water, soft drink, shampoo, and red pencil) and the spiked recoveries ranged between 94% and 97% with RSD ranging from 3% to 6%, which showed that the proposed method had satisfactory practicability and operability.

A novel magnetic composite modified with chitosan, graphene oxide and Ag nanoparticles, was successfully prepared as an efficient adsorbent for detection of rhodamine B combining with fluorescence technique.     

Synthesis and characterization of TiO2/graphene oxide nanocomposites for photoreduction of heavy metal ions in reverse osmosis concentrate

In this study, graphene oxide (GO), titanium dioxide (TiO₂) and TiO₂/GO nanocomposites were synthesized as the catalysts for photoreduction of endocrine disrupting heavy metal ions in reverse osmosis concentrates (ROC). The morphology, structure and chemical composition of these catalysts were characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, Brunauer–Emmett–Teller analysis, Barrett–Joyner–Halenda, Fourier transform infrared spectroscopy and Raman spectroscopy. The photocatalytic experiments showed that TiO₂/GO nanocomposites exhibit a higher photoreduction performance than pure TiO₂ and GO. Under the optimal conditions, the removal rates of Cd²⁺ and Pb²⁺ can reach 66.32 and 88.96%, respectively, confirming the effectiveness of photoreduction to reduce the endocrine disrupting heavy metal ions in ROC resulted from the combined adsorption–reduction with TiO₂/GO nanocomposites.

TiO₂/GO nanocomposites were synthesized successfully and exhibited an excellent ability to reduce heavy metal ions in reverse osmosis concentrate.     

Counterion coupled (COCO) gemini surfactant capped Ag/Au alloy and Ag@Au core–shell nanoparticles for cancer therapy

Hybrid silver (Ag)–gold (Au) nanoparticles (NPs) with different sizes and compositions were synthesized. Ag/Au alloy and Ag@Au core–shell type NPs were prepared from Ag and Au with various ratios using the COCO gemini surfactant, 1,6-bis (N,N-hexadecyldimethylammonium) adipate (COCOGS), 16-6-16 as a stabilizer. The formation of the Ag/Au alloy and Ag@Au core–shell was confirmed by UV-visible absorption spectroscopy, high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX) and selected area electron diffraction (SAED) patterns. Depending on the composition of the Ag/Au alloy NPs, the λ_max values varied from 408 nm to 525 nm. FTIR measurements were used to evaluate the adsorption of the COCO gemini surfactant (16-6-16) on the Ag/Au alloy and Ag@Au core–shell surface. In this present work, we study how to achieve the stability and activity of the COCO gemini surfactant (16-6-16) capped Ag/Au alloy and Ag@Au core–shell NPs for developing novel anti-cancer agents by evaluating their potentials in the Hep-2 cell line model. Thus the developed core–shell NPs were possibly involved in inducing cytotoxicity followed by inhibition of cell proliferation to the cancer cells with apoptosis induction. The developed core–shell NPs might serve as highly applicable agents in the development of next-generation cancer chemotherapeutic agents.

In this work hybrid silver (Ag)–gold (Au) nanoparticles (NPs) with different sizes and compositions were synthesized and applied for anticancer evaluations and which is effectively involved in cancer cell apoptosis through DNA damage.     

Synthesis of MOFs/GO composite for corrosion resistance application on carbon steel

Two unreported metal–organic frameworks [Cu(6-Me-2,3-pydc)(1,10-phen)·7H₂O]_n (namely Cu-MOF) and [Mn₂(2,2′-bca)₂(H₂O)₂]_n (namely Mn-MOF) were synthesized by a solvothermal method and their structures were characterized and confirmed by elemental analysis, X-ray single crystal diffraction, Fourier infrared spectroscopy and thermogravimetric analysis. Cu-MOF/graphene (Cu-MOF/GR), Cu-MOF/graphene oxide (Cu-MOF/GO), Mn-MOF/graphene (Mn-MOF/GR) and Mn-MOF/graphene oxide (Mn-MOF/GO) composite materials were successfully synthesized by a solvothermal method and characterized and analyzed by PXRD, SEM and TEM. In order to study the corrosion inhibition properties of the Cu-MOF/GR, Cu-MOF/GO, Mn-MOF/GR and Mn-MOF/GO composite materials on carbon steel, they were mixed with waterborne acrylic varnish to prepare a series of composite coatings to explore in 3.5 wt% NaCl solution by electrochemical measurements and results showed that the total polarization resistance of the 3% Cu-MOF/GO and 3% Mn-MOF/GO composite coatings on the carbon steel surface were relatively large, and were 55 097 and 55 729 Ω cm², respectively, which could effectively protect the carbon steel from corrosion. After immersion for 30 days, the 3% Mn-MOF/GO composite still maintained high corrosion resistance, the |Z| values were still as high as 23 804 Ω cm². Therefore, MOFs compounded with GO can produce a synergistic corrosion inhibition effect and improve the corrosion resistance of the coating; this conclusion is well confirmed by the adhesion capability test.

Two unreported metal–organic frameworks [Cu(6-Me-2,3-pydc)(1,10-phen)·7H₂O]_n (namely Cu-MOF) and [Mn₂(2,2′-bca)₂(H₂O)₂]_n (namely Mn-MOF) were synthesized and characterized. Cu-MOF and Mn-MOF all can form a three-dimensional structure.     

Co3O4–Ag photocatalysts for the efficient degradation of methyl orange

In this paper, a series of Co₃O₄–Ag photocatalysts with different Ag loadings were synthesized by facile hydrothermal and in situ photoreduction methods and fully characterized by XRD, SEM, TEM, FTIR spectroscopy, XPS, UV-vis and PL techniques. The catalysts were used for the degradation of methyl orange (MO). Compared with the pure Co₃O₄ catalyst, the Co₃O₄–Ag catalysts showed better activity; among these, the Co₃O₄–Ag-0.3 catalyst demonstrated the most efficient activity with 96.4% degradation efficiency after 30 h UV light irradiation and high degradation efficiency of 99.1% after 6 h visible light irradiation. According to the corresponding dynamics study under UV light irradiation, the photocatalytic efficiency of Co₃O₄–Ag-0.3 was 2.72 times higher than that of Co₃O₄ under identical reaction conditions. The excellent photocatalytic activity of Co₃O₄–Ag can be attributed to the synergistic effect of strong absorption under UV and visible light, reduced photoelectron and hole recombination rate, and decreased band gap due to Ag doping. Additionally, a possible reaction mechanism over the Co₃O₄–Ag photocatalysts was proposed and explained.

A novel Co₃O₄–Ag catalyst covered on the Ni foam substrate was synthesized via facile hydrothermal and in situ photoreduction methods for the efficient degradation of methyl orange.     

Enhanced antibacterial properties of biocompatible titanium via electrochemically deposited Ag/TiO2 nanotubes and chitosan–gelatin–Ag–ZnO complex coating

A novel double-layered antibacterial coating was fabricated on pure titanium (Ti) via a simple three-step electrodeposition process. Scanning electronic microscopy (SEM) images show that the coating was constructed with the inner layer of TiO₂ nanotubes doped with silver nanoparticles (TNTs/Ag) and the outer layer of chitosan–gelatin mixture with zinc oxide and silver nanoparticles (CS–Gel–Ag–ZnO). In comparison, we also investigated the composition, structure and antibacterial properties of pure Ti coated with TNTs, TNTs/Ag or TNTs/Ag + CS–Gel–Ag–ZnO, respectively. The TNTs was about 100 nm wide and 240 nm to 370 nm tall, and most Ag nanoparticles (Ag NPs) with diameter smaller than 20 nm were successfully deposited inside the tubes. The CS–Gel–Ag–ZnO layer was continuous and uniform. Antibacterial activity against planktonic and adherent bacteria were both investigated. Agar diffusion test against Staphylococcus aureus (S. aureus) shows improved antibacterial capacity of the TNTs/Ag + CS–Gel–Ag–ZnO coating, with a clear zone of inhibition (ZOI) up to 14.5 mm wide. Dead adherent bacteria were found on the surface by SEM. The antibacterial rate against planktonic S. aureus was as high as 99.2% over the 24 h incubation period.

A novel complex antibacterial coating fabricated via a simple three-step electrodeposition process shows high antibacterial rate of 99.2%.     

Rational design of M–N4–Gr/V2C heterostructures as highly active ORR catalysts: a density functional theory study

Inspired by the composites of N-doped graphene and transition metal-based materials as well as MXene-based materials, heterostructures (M–N₄–Gr/V₂C) of eight different transition metals (M = Ti, Cr, Mn, Fe, Co, Ni, Cu, and Zn) doped with nitrogen-coordinated graphene and V₂C as potential catalysts for the oxygen reduction reaction (ORR) using density functional theory (DFT) were designed and are described herein. The calculations showed that the heterostructure catalysts (except for Zn–N₄–Gr/V₂C) were thermodynamically stable. Ni–N₄–Gr/V₂C and Co–N₄–Gr/V₂C showed higher activities towards the ORR, with overpotentials as low as 0.32 and 0.45 V, respectively. Excellent catalytic performance results were observed from the change in electronic structure caused by the strong interaction between V₂C and the graphene layers as well as the synergistic effect between the MN₄ groups and the graphene layers. This study further provides insights into the practical application of ORR catalysts for MXene systems through the modulation of the electronic structure of two-dimensional materials.

Heterostructures (M-N₄-Gr/V₂C) of eight different transition metals (M = Ti, Cr, Mn, Fe, Co, Ni, Cu and Zn) were designed as potential catalysts for oxygen reduction reactions (ORR).     

A dopamine electrochemical sensor based on a platinum–silver graphene nanocomposite modified electrode

A platinum–silver graphene (Pt–Ag/Gr) nanocomposite modified electrode was fabricated for the electrochemical detection of dopamine (DA). Electrochemical studies of the Pt–Ag/Gr nanocomposite towards DA detection were performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The CV analysis showed that Pt–Ag/Gr/GCE had enhanced electrocatalytic activity towards DA oxidation due to the synergistic effects between the platinum–silver nanoparticles and graphene. The DPV results showed that the modified sensor demonstrated a linear concentration range between 0.1 and 60 μM with a limit of detection of 0.012 μM. The Pt–Ag/Gr/GCE presented satisfactory results for reproducibility, stability and selectivity. The prepared sensor also showed acceptable recoveries for a real sample study.

A platinum–silver graphene nanocomposite was synthesized and characterized. A nanocomposite modified electrode was fabricated in order to investigate the electrochemical detection of dopamine.     

Application of electroactive Au/aniline tetramer–graphene oxide composites as a highly efficient reusable catalyst

This study proposes a cost-effective, energy-saving, and green process that uses π–π interactions to modify graphene oxide (GO), and the conjugate structure of aniline tetramer (AT) to enhance the dispersion of GO. Au/aniline tetramer–graphene oxide (Au/ATGO) composites were synthesized and applied as a catalyst in this study. The adsorption of AT on GO, via π–π interaction, formed ATGO composites. Subsequently, the amine group on ATGO was stably anchored on Au nanoparticles (Au NPs) to form Au/ATGO composites. The Au/ATGO composites were characterized and the electroactive properties determined by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and cyclic voltammetry. The Au/ATGO composites showed excellent performance and stability as catalysts when applied for the reduction of nitrophenol to aminophenol within 225 s and the rate constant was 0.02 s⁻¹. The activation energy for the reduction of 4-NP and 2-NP was 48.10 and 68.71 kJ mol⁻¹, respectively. Following a recycling test repeated 20 times, the Au/ATGO composites maintained a conversion rate higher than 94%.

The stable and reusable Au/ATGO composites were prepared. Aniline tetramer not only modified GO but also can anchor Au NPs. The Au/ATGO composites as a catalyst exhibit good cycling stability.     

TiO2–Au composite nanofibers for photocatalytic hydrogen evolution

TiO₂-based materials for photocatalytic hydrogen (H₂) evolution have attracted much interest as a renewable approach for clean energy applications. TiO₂–Au composite nanofibers (NFs) with an average fiber diameter of ∼160 nm have been fabricated by electrospinning combined with calcination treatment. In situ reduced gold nanoparticles (NPs) with uniform size (∼10 nm) are found to disperse homogenously in the TiO₂ NF matrix. The TiO₂–Au composite NFs catalyst can significantly enhance the photocatalytic H₂ generation with an extremely high rate of 12 440 μmol g⁻¹ h⁻¹, corresponding to an adequate apparent quantum yield of 5.11% at 400 nm, which is 25 times and 10 times those of P25 (584 μmol g⁻¹ h⁻¹) and pure TiO₂ NFs (1254 μmol g⁻¹ h⁻¹), respectively. Furthermore, detailed studies indicate that the H₂ evolution efficiency of the TiO₂–Au composite NF catalyst is highly dependent on the gold content. This work provides a strategy to develop highly efficient catalysts for H₂ evolution.

The H₂ production rate of TiO₂–Au nanofibers is dramatically improved to 12 440 μmol g⁻¹ h⁻¹, 10 times that of pure TiO₂.     

Mechanistic study of N–H- and H–N-codoping of a TiO2 photocatalyst for efficient degradation of benzene under visible light

Non-metal codoping including nitrogen (N) and hydrogen (H) codoping has been emerging as an effective way to improve the performance of anatase TiO₂ in solar cell, fuel conversion and pollutant degradation. However, the mechanism of the synergistic effect of N doping and H doping on TiO₂ is still far from thorough. In this paper, N and H codoped TiO₂ nanoparticles are obtained by N doping in ammonia and then H doping in hydrogen gas, which achieves substantially boosted efficiency and reaction rate in the photocatalytic degradation of benzene under visible light excitation. The superiority of the N–H–TiO₂ photocatalyst was fully elaborated by comparing with H–N–TiO₂, which was obtained by thermal treating in H₂ and then NH₃. The reaction rate of N–H–TiO₂ in the photocatalytic degradation of benzene was nearly 2 times that of H–N–TiO₂, ∼7 times higher than that of pristine TiO₂. Furthermore, the cycling test revealed the high repeatability and stability of the N–H–TiO₂ photocatalyst. The excellent performance N–H–TiO₂ was attributed to an adequate concentration of N_iH_i defects occupying interstitial sites of the TiO₂ structure and a disordered surface layer introduced by annealing in NH₃ and H₂ successively. The synergistic effect of N–H-codoping also increased the separation and migration of electron–hole pairs triggering a photoinduced redox reaction on the surface of TiO₂.

The crystallinity, N_iH_i dopants and disordered surface layer are of importance to N–H–TiO₂ when comparing with the structure and properties of H–N–TiO₂.     

Synthesis of silver particles stabilized by a bifunctional SiHx–NHy–PMHS oligomer as recyclable nanocatalysts for the catalytic reduction of 4-nitrophenol

Bifunctional oligomers with both reducing and stabilizing functionalities were prepared and successfully applied to the preparation of silver colloids of around 2 nm size without employing a strong stabilizer such as S and P, which was quite difficult to achieve. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) were performed to determine the morphology and particle size of the Ag colloids. UV-vis spectroscopy and X-ray absorption spectroscopy (XAS) were implemented to investigate the oxidation state of the Ag colloids. Synthesis parameters such as the density control of the ligating functionalities, the propinquity of the reducing and stabilizing groups, the extent of ligand stabilization and the reducing rates were found to have important effects on the formation and stabilization of Ag colloids. The as-synthesized Ag colloids were very stable even after being deposited on silica; then, they were subjected to calcination to get rid of the organics, which afforded Ag NPs (1.9–3.5 nm) on silica with narrow size distribution. These Ag NPs performed excellently in catalytic 4-nitrophenol reduction with conversion of up to 98% within 10 min. Furthermore, the Ag nanoparticles were quite stable and exhibited excellent reusability for seven successive reaction cycles without obvious decay. The straightforward synthesis of the ultra-small and stable Ag NPs has the potential for applications in the synthesis of other supported late transition metals.

A novel strategy using bifunctional SiH_x–NH_y–PMHS without using strong stabilizers was applied to synthesize Ag NPs of around 2 nm size.